Hamburg Cocoa Symposium
Kuehne Logistics University 12th May 2017 Hamburg/Germany
Reinhard Matissek
MOSH/MOAH
in Cocoa and Chocolate
» 3 Years Research «
Food Chemistry Institute of the Association of the German Confectionery Industry (BDSI), Cologne/Germany
Lebensmittelchemisches Institut des Bundesverbandes der Deutschen Süßwarenindustrie (BDSI), Köln/Germany
MOSH/MOAH Joint Research Project – Set up
project start: 1.7.2013
2nd period: cocoa
31.12.2017
1st period: all
30.6.2016
Stiftung der Deutschen Kakao- und Schokoladenwirtschaft
Total Costs ≈ 1 Mio. €
Bundesverband der Deutschen Süßwarenindustrie BDSI Association of the German Confectionery Industry Foundation of the German Cocoa and Chocolate Industry
MOSH/MOAH
to minimise as far as possible
development
of a
toolbox
Joint Research Project – Objectives
Brief Chemistry Mineral Oil vs. Edible Oil
Edible Oil
obtained from plants or animals
triglycerides
digestible
saponifiable
Mineral Oil
obtained from crude oil
also produced synthetically from coal, natural gas or biomass
indigestible
unsaponifiable
fatty acids g
lyce
rol
carbon atom numbers: C16–C40(50)
C = Carbon H = Hydrogen
The correct term
Source: EFSA Journal 2012 / BfR 2009
Mineral Oil Hydrocarbons (MOH) – Classification
Source: EFSA Journal 2012 / BfR 2009
Myriads of Single Substances
Hazelnut kernels Hazelnut kernels
MOSH hump
MOAH hump
4 : 1
Composition classically found in Foods
Impact on Health
Source: EFSA Journal 2012 / BfR 2009
Komponenten aus Mineralöl
Mineral Oil Ordinance 4th Draft of 24.2.2017
Regulation of the Migration of MOAH*
Migration limit is valid only for Food Contact Materials (FCM) made
from waste paper material
A general limit in foods, which applies for all contamination sources, is not provided
Mandatory of Barrier
Obligation to use a functional barrier
If barrier, then migration of MOAH = not detectable (LOQ: 0.5 mg/kg food / food simulant)
Exeptions from barrier engagement
MOSH-Regulation is not longer included
problems of definitional and analytical differentiation
Entry into Force
open
*MOAH: high alkylated aromatic hydrocarbons C16–C35; one or more rings
LOQ: Limit of Quantitation
New! Only valid in Germany!
Based on the Scientific Opinion on Mineral Oil Hydrocarbons in Food [EFSA Journal 2012;10(6):2704]
Adressing Member States – „with the active involvement of the food business operators“
Collection of Data: Including chocolate and cocoa (as well as food contact materials for these products)
Where MOSH/MOAH are detected in food, Members States should carry out investigations to determine possible sources
Analytical method (CEN) is only related to fats and oils EU-wide coordination of analytics by JRC
EU Monitoring MOSH/MOAH Commission Recommendation (EU) 2017/84 of 16 January 2017
Systematic Approach From raw material to ...
GCxGC-MS-ToF
online LC-GC-FID
Detection, Characterisation and Tracking of Entry Sources
Surveying the humps
[Quantitation]
Surveying the finger prints
[Characterisation] Creating a
database
Scientific Approach The State-of-the-Art Methodology
__________________________________________________________________________________________________________ LC Liquid Chromatography; GC Gas Chromatography, FID: Flame Ionisation Detector; TOF: Time-of-Flight; MS: Mass Spectrometry
Online LC-GC-FID Method
The most important Milestone
Milestone 1: Systematic Approach
Controlled Use/Residues:
• Microcrystalline Waxes
• Bees wax / Carnauba wax
• Pesticide Formulations
• Dust-binding Agents
• Anti-foam / Release Agents
Food Contact Materials:
• Cardboards and corrugated Cardboard made from Recycled Fibres
• Printing Inks
• Jute / Sisal Sacks
• Hotmelts
Accidental:
• Environment
• Lubricants / Hydraulic Oils
• Compressed Air
• Particulate Matter from Paved Roads
• Car Exhausts
In the Beginning: Focusing only on End Products
Migration = Wandering of Substances from Packaging into Foodstuff
Migration from packagings made with recycling paper
MOSH/MOAH Migration – Well known Sources Food Contact Materials – End Products Packagings
Migration from packagings with mineral oil based printing inks
Cross Migration from outer packaging (cardboard/corrugated board/carton)
via gas phase Migration – MOSH/MOAH≤C25 at room temperature
via direct contact Migration – MOSH/MOAH≤C35
via indirect contact Permeation through thin layers – MOSH/MOAH≤C35
Migration Process via Gas Phase
Evaporation at Room Temperatur
(MOH <C25)
Transport into Gas Phase
Recondensation into Food
Car
db
oar
d
Car
db
oar
d
Migration Process (schematical)
Secondary (Transport) Packaging
Other Packages
Primary Packaging
Functional Barrier
Food
Environment
Migration Process – Influences
Amount of Substances
which are capable of Migration
Functional Barrier (e.g. aluminium foil,
PET)
Duration
Temperature Properties
of the Food
Tempory Barrier (e.g. PE, PP)
___________________________________________________
PE Polyethylene; PP Polypropylene; PET Polyethylenterephthalate
The most important Milestone
Prior Migration
Identified Main Sources: Use of Recycled Cardbord
Use of not really mineral oil free Bags (Jute/Sisal, Inks)
Milestone 2: Prior Migration
Shipping Container: Transport of Coffee, Cocoa, Nuts, Rice
Quelle: Matissek 2013 Quelle: http://vnfoodco.com/ images/042012/IMG_2239.jpg
Quelle: http://legroupindustries.com/wp-content/uploads/2013/05/25kg-bags-LE-Group-Industries.jpg
Rice
Coffee
Cocoa
Dressings
Jute Sacks
PP Bags
Jute Sacks – Food Grade Quality?
According to the International Jute Organisation – IJO (1998)
o Objectives: Substitution of mineral oils in jute sacks by vegetable oils
o No toxic substances allowed
o Definition of „Unsaponifiable Matter (USM)“ as an (unspecific) quality parameter was introduced
o Specification of analytical method
o USMmax=1,250 mg/kg Jute
Jute Sack Study
0
500
1.000
1.500
2.000
2.500
3.000
3.500
4.000
4.500
5.000
1 2 3 4 5 6 7 8 9 10 11
US
M r
esp.
MO
AH
resp. M
OA
H [
mg/k
g]
Sample No.
1,250 mg/kg Jute
ΣMOSH/MOAH = C10 ̶ C50 USM ΣMOAH ΣMOSH
„Food Grade“ Jute Sacks can exceed the IJO Maximum level
They can contain remarkable amounts of MOSH/MOAH
Unused „Food Grade“ Jute Sacks (2013─2016) Unused Jute Sack with mineral oil containing Batching oil (from 1995)
____________________________ IJO International Jute Organisation
Transport of Cocoa in Shipping Containers Criss-Cross Exchange
ca. 100 kg Dressing
ca. 500 kg Jute Fibres 25.000 kg Cocoa Beans
23–1.710
.n.n.–130
54–610
MO
H
[mg
/kg]
M
OH
[m
g/k
g]
MO
H
[mg
/kg]
n=
94
n
= 1
6
n=
32
MOH = ∑MOSH/MOAH
Quelle: Matissek 2013
cocoa seads
port of arrival
cocoa processor
c. liquor c. butter
c. powder
end product
consumer
From „Bean to Bar“
environment
deso
jute / board
conche
shells
rosting
Lubricants Lubricants lubricants
food contact materials
No MOSH! No MOAH!
Discharges Entries
Commodities Overview – MOSH
MOSH sorted by increasing order / MOAH sorted by increasing order MOSH-Content as well / * N>LOQ
MOSH/MOAH Contents in various Food Raw Materials
/ 2013–2016
MOSH/MOAH occur in the environment
all around us and can therefore migrate into foods in very
different ways
Main source of migration of MOSH/MOAH
into both raw materials and foods:
printing inks in recycled cardboard
boxes, paper and corrugated cardboards
Another importance source of entry:
Jute Bags
Key Findings: In General
Jute Bags are used along the whole cocoa supply chain
from farm to factory
Approved Jute Bags („Food Grade Quality“) are not
MOSH/MOAH free
Migration of MOSH/MOAH via Jute Bags has to be
avoided from the beginning
Key Findings: Jute Bags
©Matissek, 2013 ©Erbrath, 2013 ©Romano, 2013
Minimisation of the intake of MOSH/MOAH through finished
products: BDSI TOOLBOX (continously updated – including recommendations):
Fresh fibre packaging
Mineral oil free inks
Use of barriers in packaging
others
Actions: In General
Minimise the intake of MOSH/MOAH through
commodities and semi-finished products:
No contact with mineral oil components in the supply chain of cocoa (and other raw materials)
Mineral oil free shipment/transport
Mineral oil free jute/sisal bags
Actions: Minimisation in the Cocoa Sector
©Matissek, 2003
The most important Milestone
Milestone 3: The Master Plan
RESEARCH
COORDINATION EVIDENCE
COLLECTION
DATABASE
OPERATORS
FOOD
CHAIN
MINIMIZATION
KNOWLEDGE EXPERTISE IMPULSES OBJECTIVES
GLOBAL TOOLBOX
1st Part: Research Work 2nd Part: Implementation Work